Thermoplastic gel compositions and their methods of making

ABSTRACT

Methods and compositions are provided for preparation of thermoplastic gels. The compositions have a base composition including a thermoplastic gel and a softener oil and the gel has a hardness between 15 Shore 000 and 65 Shore 000. The gel may also include an additive, such as a mineral filler, an anti-tack agent, and a mixture of a mineral filler and an anti-tack agent. The softener oil may be a high molecular weight oil having a molecular weight greater than about 250 g/mol.

This application is being filed on Jan. 9, 2015, as a PCT InternationalPatent application and claims priority to U.S. Patent Application Ser.No. 61/925,707 filed on Jan. 10, 2014, the disclosure of which isincorporated herein by reference in its entirety.

BACKGROUND

Processing thermoplastic rubber gel sealants in a cost effective andefficient manner has presented its challenges. As technology progresses,sealants will be subjected to increasingly higher temperatureenvironments and more demanding performance requirements. There hasbeen, and there presently exists, a need for high performance sealantsto meet these demands. For example, there is an increasing need for highservice gel sealants for use in outdoor energy transmission applicationsand for use near or inside engine compartments.

In particular, closure systems are used to protect internal componentsfrom degradation caused by external environments. For example,components related to the connections of fiber optics cables, coaxialcables, and copper cables are often enclosed in closure systems.Examples of commercially available closure systems include Fiber OpticsSplice Closures (FOSC), the Outdoor Fiber Drop Repair (OFDR), theOutdoor Fiber Distribution Closure (OFDC), and the Fiber opticInfrastructure System Technology (FIST). Additional commerciallyavailable closure systems include copper joints such as Mechanical JointClosure (MJC), Toolless Torchless Reentrable Closure (TTRC), and Coaxconnector closures (GSIC) available from TE Connectivity. These types ofclosures can be used in aerial, pedestal, and underground environments.Other closure systems are commercially available for use withcommunication and energy transmission cables.

Closure systems typically include internal components such as fiberorganizers, cable seals and termination devices, drop cable seals for anumber of drops with drop cable termination devices, universal spliceholders for a number of splices, and copper and coax connections. Cablejoints may be subject to environmental factors such as varying moisturelevels, heat and cold, and exposure to other chemical substances, so theinternal components and connections will require appropriate protectionfrom these elements. The closure systems are preferably protected fromdamage with a sealant of some sort. Conventional sealants, however,suffer from a number of drawbacks that make them less suitable forcertain closure systems.

Sealants are often used for insulation and for protection against water,corrosion and environmental degradation, and for thermal management. Anumber of sealants are known but currently available sealants havecertain drawbacks and disadvantages that make them inadequate forspecific uses and for use in contact with certain materials. Inparticular, there is an unmet need for sealants that are suitable forthe latest types of fiber optic and electronic closure systems.

Suitable sealing systems for closures are needed for use with a varietyof different cables. Traditionally, thermoplastic elastomer gels (TPEGs)have been used as sealants in certain applications due to their uniqueproperties. TPEGs have provided many years of reliable in-fieldperformance for applications requiring a low maximum service temperatureof approximately 70° C. TPEGs may comprise a styrene ethylene/butylenestyrene (“SEBS”) copolymer swollen with an oil softener (e.g., mineral,synthetic, or vegetable oil softeners). A problem, however, withthermoplastic gels used as sealants, and in closure systems in general,is that they often contain high amounts of mineral oil. Conventionalthermoplastic gels typically exhibit 20 to 30 wt % oil bleed out.Accordingly there exists an unmet need for gels, sealants, and closuresystems with suitable hardness, viscoelastic properties, long-termperformance (e.g., >20 years), amongst other properties, including lowoil bleed out, better processability by improved melt viscosity, lowershrinkage, and better thermal conductivity.

SUMMARY

Novel thermoplastic gel compositions are disclosed herein. In oneaspect, the thermoplastic gel comprises a base composition consisting ofa thermoplastic rubber and softener oil. The gel further comprises atleast one additive selected from the group consisting of a mineralfiller, an anti-tack agent, and mixtures thereof, wherein the basecomposition and at least one additive define an overall composition, andwherein the gel has the following properties: (a) a hardness between 15Shore 000 and 65 Shore 000; and (b) less than 10% oil bleed out afterbeing under compression of 1.2 atm for 60 days at 70° C.

In a second aspect, the thermoplastic gel comprises a base compositionconsisting of a thermoplastic rubber and a softener oil, wherein thesoftener oil is a high molecular weight oil having a molecular weightgreater than 250 g/mol, and wherein the gel has the followingproperties: (a) a hardness between 15 Shore 000 and 65 Shore 000; and(b) less than 10% oil bleed out after being under compression of 1.2 atmfor 60 days at 60° C.

In a further aspect, the thermoplastic gel comprises a base compositionconsisting of a thermoplastic rubber and a softener oil, wherein thesoftener oil is a high molecular weight oil having a molecular weightgreater than 250 g/mol, and wherein the gel has the followingproperties: (a) a hardness between 30 Shore 000 and 45 Shore 000; and(b) less than 10% oil bleed out after being under compression of 1.2 atmfor at least 26 days at 70° C.

In some embodiments, a thermoplastic gel is provided comprising a basecomposition consisting of a thermoplastic rubber and a softener oil; andat least one additive selected from the group consisting of a mineralfiller, an anti-tack agent, and mixtures thereof, wherein the basecomposition and at least one additive define an overall composition, andwherein the gel has a hardness between 15 Shore 000 and 65 Shore 000. Insome embodiments, the gel exhibits less than 20 wt %, less than 15 wt %,or less than 10 wt % oil bleed out after being under compression of 1.2atm for at least 25 days at 70° C.

In some embodiments, a thermoplastic gel is provided comprising athermoplastic rubber comprising a styrenic block copolymer. In someaspects, the styrenic block copolymer is astyrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrenecopolymer.

In some embodiments, a thermoplastic gel is provided comprising amineral filler between 0.1 wt % and 50 wt % of the overall composition.In some embodiments, the mineral filler is selected from the groupconsisting of talc, calcium carbonate, clay, wollastonite, silicates,glass, and combinations thereof. In a specific embodiment, the mineralfiller is talc. In some aspects, the talc is present in approximately 30wt % of the overall composition.

In some embodiments, a thermoplastic gel is provided comprising ananti-tack agent between 0.1 wt % and 10 wt % of the overall composition.In some embodiments, the gel composition comprises the anti-tack agentis selected from the group consisting of a silicone, silane, siloxane,or copolymer thereof.

In some embodiments, a thermoplastic gel is provided comprising amineral filler selected from the group consisting of talc, calciumcarbonate, clay, wollastonite, silicates, glass, and combinationsthereof, and an anti-tack agent selected from the group consisting of asilicone, silane, siloxane, or copolymer thereof; and wherein themineral filler is between 0.1 wt % and 50 wt % of the overallcomposition and the anti-tack agent is between 0.1 wt % and 10 wt % ofthe overall composition.

In some embodiments, a gel composition is provided that comprises athermoplastic rubber comprising (a) a base polymer having at least onefunctional group capable of crosslinking, (b) a functionalized extender,and (c) an optional crosslinker having multiple functional groups thatare compatible and willing to react with the functional groups in thebase polymer or the functionalized extender.

In some embodiments, a gel composition is provided that comprises asoftener oil that is a high molecular weight oil having a molecularweight greater than 250 g/mol. In some embodiments, the gel compositioncomprises a high molecular weight oil is derived from one of thefollowing: a mineral oil, a paraffin oil, a naphthenic oil, an aromaticoil, a poly-alpha olefin, or a combination thereof.

In some embodiments, a gel composition is provided that comprises asoftener oil hat is a high molecular weight oil and a mineral fillerselected from the group consisting of talc, calcium carbonate, clay,wollastonite, silicates, glass, and combinations thereof and wherein themineral filler is between 0.1 wt % and 50 wt % of the overallcomposition. In some aspects, the mineral filler is talc, and whereinthe talc comprises approximately 30 wt % of the overall composition.

In some embodiments, a thermoplastic gel is provided comprising asoftener oil hat is a high molecular weight oil and an anti-tack agentselected from the group consisting of a silicone, silane, siloxane, orcopolymer thereof; and wherein the anti-tack agent is between 0.1 wt %and 10 wt % of the overall composition.

In some embodiments, a thermoplastic gel is provided comprising anadditional additive selected from the group consisting of: flameretardants, coloring agents, adhesion promoters, dispersants, flowimprovers, plasticizers, toughening agents, and combinations thereof.

In some embodiments, a thermoplastic gel is provided comprising astabilizer at between 0.1 wt % and 5 wt % of the overall composition,wherein the stabilizer is selected from the group consisting of anantioxidant, acid-scavenger, light and UV absorber/stabilizer, heatstabilizer, metal deactivator, free radical scavenger, carbon black,antifungal agent, and mixtures thereof.

In another embodiment, a thermoplastic gel is provided comprising a basecomposition consisting of a thermoplastic rubber and a softener oil,wherein the softener oil is a high molecular weight oil having amolecular weight greater than 250 g/mol, and wherein the gel has ahardness between 15 Shore 000 and 65 Shore 000, and wherein the gelexhibits less than 10% oil bleed out after being under compression of1.2 atm for 26 days at 70° C.

In another embodiment, a thermoplastic gel is provided comprising a basecomposition consisting of a thermoplastic rubber and a softener oil,wherein the softener oil is a high molecular weight oil derived from amineral oil, a paraffin oil, a naphthenic oil, an aromatic oil, apoly-alpha olefin, or a combination thereof. In some aspects, thesoftener oil is a high molecular weight oil derived from a paraffin oil,a naphthenic oil, an aromatic oil, a poly-alpha olefin, or a combinationthereof. In some embodiments, a thermoplastic gel is provided comprisinga softener oil that is a high molecular weight oil derived from amineral oil, a paraffin oil, a naphthenic oil, an aromatic oil, apoly-alpha olefin, or a combination thereof.

In some embodiments, a method of making a thermoplastic gel is providedcomprising mixing a base composition consisting of a thermoplasticrubber, a softener oil, and at least one additive selected from thegroup consisting of a mineral filler, an anti-tack agent, and mixturesthereof, wherein the base composition and at least one additive definean overall composition; and providing heat to form the thermoplasticgel, wherein the resultant thermoplastic gel has a hardness between 15Shore 000 and 65 Shore 000.

In some embodiments, a method for making a thermoplastic is providedwherein the gel exhibits less than 20 wt %, less than 15 wt %, or lessthan 10 wt % oil bleed out after being under compression of 1.2 atm forat least 25 days at 70° C.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a depiction of an interconnect system having a connection hubhaving multiple connection ports or receptacles for the connector,housing, and cable components to be connected.

FIG. 2 is a depiction of a connector, housing, and cable assembly withradial sealing.

FIG. 3 is a depiction of a connector, housing, and cable assembly withaxial sealing.

FIGS. 4a and 4b are depictions of a straight two piece housing assemblydesigned for axial sealing.

FIGS. 5a and 5b are depictions of an angled two piece housing assemblydesigned for axial sealing.

FIG. 6 is a side view of a telecommunications enclosure suitable forusing a sealant in accordance with the principles of the presentdisclosure.

FIG. 7 is an end view of the telecommunications enclosure of FIG. 6.

FIG. 8 is an exploded view of the telecommunications enclosure of FIG.6.

FIG. 9 is a cross-sectional view taken along section line 9-9 of FIG. 7.

FIG. 10 is a cross-sectional view taken along section line 10-10 of FIG.6.

FIG. 11 is a graph of oil bleed out showing extender wt loss (%) vs.days of 120 kPa pressure at 70° C. for representative thermoplastic gelexamples and a comparative gel example.

DETAILED DESCRIPTION

As used herein, terms such as “typically” are not intended to limit thescope of the claimed invention or to imply that certain features arecritical, essential, or even important to the structure or function ofthe claimed invention. Rather, these terms are merely intended tohighlight alternative or additional features that may or may not beutilized in a particular embodiment of the disclosure.

As used herein, “mix,” “mixed,” or “mixture” refers broadly to anycombining of two or more compositions. The two or more compositions neednot have the same physical state; thus, solids can be “mixed” withliquids, e.g., to form a slurry, suspension, or solution. Further, theseterms do not require any degree of homogeneity or uniformity ofcomposition. Thus, such “mixtures” can be homogeneous or heterogeneous,or can be uniform or non-uniform. Further, the terms do not require theuse of any particular equipment to carry out the mixing, such as anindustrial mixer.

As used herein, “optionally” means that the subsequently describedfeature(s) or event(s) may or may not be present or occur. For example,in some embodiments, an optional event may not occur. In otherembodiments, the optional event occurs one or more times.

As used herein, “comprise,” “comprises,” “comprising,” or “comprised of'refer to groups that are open, meaning that the group can includeadditional members in addition to those expressly recited. For example,the phrase, “comprises A” means that A must be present, but that othermembers can also be present. The terms “include,” “have,” “contain,” and“composed of,” and their grammatical variants, have the same meaning. Incontrast, “consist of,” “consists of,” or “consisting of' refer togroups that are closed. For example, the phrase “consists of A” meansthat A and only A is present.

As used herein, “or” is to be given its broadest reasonableinterpretation, and is not to be limited to an either/or construction.Thus, the phrase “comprising A or B” means that A can be present and notB, or that B is present and not A, or that A and B are both present.Further, if A, for example, defines a class that can have multiplemembers, e.g., A1 and A2, then one or more members of the class can bepresent concurrently.

As used herein, “providing” is to be construed as having its broadestreasonable scope. For example, providing a composition that comprises aparticular compound includes, but is not limited to, adding the compoundto the composition, generating the compound in the composition via achemical reaction, or receiving the composition, e.g., as the product ofanother process.

As used herein, the term “polymer” may refer to a polymeric compoundprepared by polymerizing monomers, whether of the same or a differenttype. The generic term “polymer” embraces the terms “homopolymer,”“copolymer,” “terpolymer,” and the like.

As used herein, the term “base composition” may refer to thethermoplastic gel composition consisting of (1) thermoplastic rubbercomprising a base polymer and optionally a functionalized extenderand/or crosslinker, and (2) softener oil.

As used herein, the term “overall composition” or “overall thermoplasticgel composition” may refer to the combination of the base compositionand any additives or components in addition to the base composition,such as (but not limited to) stabilizers, mineral fillers, and/oranti-tack agents.’

As used herein, the term “high molecular weight oil” may refer to asoftener oil composition having a molecular weight greater than about250 g/mol. In some embodiments, the high molecular weight oil has amolecular weight greater than 250 g/mol, 400 g/mol, or 500 g/mol, andless than 2,000 g/mol, 1,500 g/mol, 1,200 g/mol, 1,000 g/mol, 900 g/mol,800 g/mol, 700 g/mol or 600 g/mol. In some embodiments, the highmolecular weight oil has a molecular weight between 250 g/mol and 1,500g/mol, between 400 g/mol and 900 g/mol, or between 500 g/mol and 800g/mol.

As used herein, the term “functionalized extender” may refer to anycompound having a functional group that is compatible and willing toreact with a functional group in the base polymer or thecrosslinker/coupling agent. In certain embodiments, the term refers toany compound comprising a single functional site that is capable offorming a connection to a base polymer or a crosslinker/coupling agent.In certain embodiments, the functionalized extender is a maleatedextender, such as maleated polyisobutylene.

Any concentration range, percentage range, or ratio range recited hereinis to be understood to include concentrations, percentages, or ratios ofany integer within that range and fractions thereof, such as one tenthand one hundredth of an integer, unless otherwise indicated. Also, anynumber range recited herein relating to any physical feature are to beunderstood to include any integer within the recited range, unlessotherwise indicated. It should be understood that the terms “a” and “an”as used above and elsewhere herein refer to “one or more” of theenumerated components. For example, “a” polymer refers to one polymer ora mixture comprising two or more polymers.

In certain embodiments, the thermoplastic gel composition comprises: (1)a thermoplastic rubber comprising a base polymer and optionally afunctionalized extender and/or crosslinker, (2) a softener oil, and (3)optionally, various additives. In order to improve the processability ofthese gel compositions, as well as extend their functional capabilities,the thermoplastic rubber, the softener oil, and the optional additivesmay be blended together in order to improve or maintain thermoplasticgel properties, such as reduced tackiness, lower melt temperature ormelt viscosity, improved thermal conductivity (to reduce cooling time inthe mold), or same or improved oil retention under pressure (i.e.,reduced oil bleed out).

In some embodiments, the softener oil in the gel composition is a highmolecular weight oil. In some embodiments, the additive comprises amineral filler. In other embodiments, the additive comprises ananti-tack agent. Additionally, in certain embodiments, the gelcomposition includes the combination of (1) a high molecular weight oiland a mineral filler additive, (2) a high molecular weight oil and ananti-tack agent additive, (3) mineral filler and anti-tack agentadditives, or (4) a high molecular weight oil combined with mineralfiller and anti-tack agent additives.

In some embodiments, a thermoplastic gel composition is providedcomprising 50-80 wt % synthetic hydrocarbon softener oil, 15-30 wt %thermoplastic rubber comprising a styrenic-rubber block copolymer, and0.1-5 wt % of a stabilizer. In some embodiments, the synthetichydrocarbon softener oil is a high molecular weight oil.

In some embodiments, a thermoplastic gel composition is providedcomprising 50-80 wt % of a softener oil, 10-30 wt % thermoplastic rubbercomprising a styrenic-rubber block copolymer, and at least one additiveselected from the group consisting of a mineral filler, an anti-tackagent, and mixtures thereof. In some embodiments, the softener oil is awhite mineral oil or a

In some embodiments, a thermoplastic gel is provided by a methodcomprising mixing the components to form a composition, and heating thecomposition to form a thermoplastic gel, wherein the thermoplastic gelexhibits less than about 20, 15 or 10 wt % oil bleed out undercompression of 120 kPa (1.2 atm) at 70° C. over a period of about 25,30, 45 or 60 days.

In some embodiments, thermoplastic gels are provided that exhibit aShore 000 hardness of from 30 to 45; a range of stress relaxation (60 svalue) of from 12-30%; a tensile strength in a range from 0.40 to 1 MPa;and an elongation to Break (%) in a range from 1000-2300%.

In some embodiments, thermoplastic gels are provided that exhibit lessthan 20 wt %, less than 15 wt % oil bleed out, or less than 10 wt % oilbleed over a period of 60 days under compression of 1.2 atm at 70° C.

In some embodiments, thermoplastic gels are provided that exhibit lessthan less than 10 wt % oil bleed out over a period of at least 25 daysunder compression of 1.2 atm at 70° C.

In some embodiments, thermoplastic gels are provided that are preparedfrom a composition comprising a thermoplastic rubber and a softener oil,and at least one additive selected from the group consisting of amineral filler, an anti-tack agent, a stabilizer, and mixtures thereof,wherein the gels exhibit less than 10 wt % oil bleed out under 120 kPaat 70° C. over a period of at least 26 days, while retaining favorablegel properties including a range of Shore 000 hardness of from 32 to 44;and a range of stress relaxation (60 s value) of from 13-28%; a tensilestrength in a range from 0.41 to 1 MPa; and elongation to Break (%) in arange from 1000-2300%. In some embodiments, the softener oil is a highmolecular weight synthetic hydrocarbon.

In some embodiments, methods of making thermoplastic gels are provided,comprising mixing a composition comprising a thermoplastic rubber and asoftener oil, and at least one additive selected from the groupconsisting of a mineral filler, an anti-tack agent, a stabilizer, andmixtures thereof; and heating the composition to form the thermoplasticgels, wherein the gels exhibit less than 10 wt % oil bleed out under 120kPa at 70° C. over a period of at least 26 days, while retainingfavorable gel properties including a range of Shore 000 hardness of from32 to 44; and a range of stress relaxation (60 s value) of from 13-28%;a tensile strength in a range from 0.41 to 1 MPa; and elongation toBreak (%) in a range from 1000-2300%. In some embodiments, the softeneroil is a high molecular weight synthetic hydrocarbon.

In some embodiments, thermoplastic gels are provided comprising athermoplastic rubber and a softener oil, and at least one additiveselected from the group consisting of a mineral filler, an anti-tackagent, a stabilizer, and mixtures thereof, wherein the gels exhibit lessthan 10 wt % oil bleed out under 120 kPa at 70° C. over a period of atleast 26 days, while retaining favorable gel properties including arange of Shore 000 hardness of from 32 to 44; and a range of stressrelaxation (60 s value) of from 13-28%; a tensile strength in a rangefrom 0.41 to 1 MPa; and elongation to Break (%) in a range from1000-2300%. In some embodiments, the softener oil is a high molecularweight synthetic hydrocarbon.

Making the Thermoplastic Gel

In one embodiment, a method of making a thermoplastic gel is provided,comprising mixing a base composition consisting of a thermoplasticrubber, a softener oil and at least one additive selected from the groupconsisting of a mineral filler, an anti-tack agent, a stabilizer, andmixtures thereof, wherein the base composition and at least one additivedefine an overall composition, and providing heat to the overallcomposition to form the thermoplastic gel; wherein the resultantthermoplastic gel exhibits a hardness between 15 Shore 000 and 65 Shore000. In some embodiments, the thermoplastic gel exhibits a hardnessbetween 30 Shore 000 and 45 Shore 000. In some embodiments, athermoplastic gel made by the method exhibits less than 20 wt %, lessthan 15 wt %, or less than 10% oil bleed out after being undercompression of 1.2 atm for a time period of over 25 days (600 hrs) at70° C.

In some embodiments, a method of making a thermoplastic gel is provided,comprising mixing a base composition consisting of a thermoplasticrubber comprising a softener oil and at least one additive selected fromthe group consisting of a mineral filler, an anti-tack agent, andmixtures thereof, wherein the base composition and at least one additivedefine an overall composition, and providing heat to the overallcomposition to form the thermoplastic gel.

In further embodiments, a method of making a thermoplastic gel isprovided comprising mixing a base composition consisting of athermoplastic rubber and a softener oil, wherein the softener oil is ahigh molecular weight oil having a molecular weight greater than 250g/mol, and providing heat to the overall composition to form thethermoplastic gel, wherein the gel has a hardness between 15 Shore 000and 65 Shore 000.

In certain embodiments, the thermoplastic gel composition is made by amethod comprising blending a base composition of thermoplastic rubberand softener oil at ambient temperature. In some embodiments, the basecomposition is made by a method comprising mixing (1) greater than 1 wt%, 2 wt %, 3 wt %, 4 wt %, or 5 wt %, and less than 50 wt %, 45 wt %, 40wt %, 35 wt %, 30 wt %, 25 wt %, 20 wt %, or 15 wt % of thethermoplastic rubber with (2) greater than 50 wt %, 60 wt %, 70 wt %, or80 wt %, and less than 99 wt %, 95 wt %, 90 wt %, or 85 wt % of thesoftener oil, wherein the combined wt % of the thermoplastic rubber andsoftener oil add up to 100 percent of the base composition. In someembodiments, the base composition is made by a method comprising mixingapproximately 1-49 wt %, 5-40 wt %, or 5-20 wt % of a thermoplasticrubber with approximately 51-99 wt %, 50-80 wt %, 60-95 wt %, or 80-95wt % of a softener oil, wherein the combined wt % of the thermoplasticrubber and softener oil add up to 100 percent of the base composition.

In certain embodiments, the method of making comprises mixing the gelcomponents together at an elevated temperature (i.e., greater than roomtemperature) for a certain period of time. The temperature and time attemperature may be adjusted accordingly to target the end propertiesdesired in the gel. Several of those properties are discussed in thesection below labeled “Uses and Properties of the Thermoplastic Gel, andTesting Methods.” In certain embodiments, the mixing and reacting isconducted at an elevated temperature between about 100-250° C., about150-220° C., about 180-200° C., or about 200-250° C. Typically, themixing and reacting is not conducted at a temperature that is above theflashpoint of any of the components.

In some embodiments, the mixing at the elevated temperature is held fora period of time greater than approximately 1 minute, 5 minutes, 10minutes, 30 minutes, 1 hour, 2 hours, or 3 hours, and less than 24hours, 12 hours, 8 hours, or 6 hours. In some embodiments, the mixing atthe elevated temperature is held for a period of time of approximately10 minutes, 30 minutes, or between 1 minute and 24 hours, 1-12 hours,2-8 hours, or 3-6 hours. In some embodiments, the period of time is onthe order of approximately 1 minute, 5 minutes, 10 minutes, 30 minutesor 1 hour, and processing/mixing is conducted via injection molding of apre-blended slurry, which may be more cost effective and avoiddegradation of the composition.

In certain embodiments, the thermoplastic rubber comprises a basepolymer that has been reacted with a functionalized extender and/orcrosslinker component to extend the length or add side chains to thebase polymer. In some embodiments, no catalyst or initiator is neededother than heat to react the base polymer, functionalized extender,and/or crosslinker together. For example, certain ionic crosslinkers(described below in greater detail) may only need heat and time to reactand form the gel component. In other embodiments, a catalyst orinitiator may be used to react the base polymer, functionalizedextender, and/or crosslinker together.

In some embodiments, no functionalized extender component is employed inthe thermoplastic rubber.

In some embodiments, no crosslinker component is employed in thethermoplastic rubber.

In certain embodiments, at least one additive is added to the basecomposition, wherein the at least one additive is between about 0.1-75wt % of the overall composition (i.e., base composition plus additives),about 1-50 wt % of the overall composition, about 5-40 wt % of theoverall gel composition, about 15-30 wt % of the overall composition,about 0.1-10 wt % of the overall gel composition, about 0.5-5 wt % ofthe overall gel composition, or about 1-3 wt % of the overall gelcomposition.

In one embodiment, the at least one additive is a mineral filler,wherein the filler is between about 0.1-50 wt % of the overallcomposition, about 5-40 wt % of the overall gel composition, or about15-30 wt % of the overall composition. In another embodiment, ananti-tack agent is added to the gel composition, wherein the anti-tackagent is between about 0.1-10 wt % of the overall gel composition, about0.2 and 5 wt % of the overall composition, or about 0.5 and 2 wt % ofthe overall composition. In yet another embodiment, one or morestabilizer agents are added to the gel composition. Further potentialadditives are described in further detail below.

Base Polymer/Thermoplastic Rubber

In some embodiments, the thermoplastic rubber comprises greater than 1wt %, 2 wt %, 3 wt %, 4 wt %, or 5 wt %, and less than 50 wt %, 45 wt %,40 wt %, 35 wt %, 30 wt %, 25 wt %, 20 wt %, or 15 wt % of the basecomposition. In other embodiments, the thermoplastic rubber comprisesapproximately 1-49 wt %, 5-40 wt %, or 5-20 wt % of the base composition

In certain embodiments, the base polymer in the thermoplastic rubber isa styrenic-rubber block copolymer (e.g. diblock and triblock polymers).In certain embodiments, the styrenic block copolymer is astyrene-ethylene/butylene-styrene (“SEBS/SEB”),styrene-ethylene/propylene-styrene (“SEPS/SEP”) copolymer or styrenebutadiene styrene (SBS/SB). In yet other embodiments, the base polymeris an olefinic block copolymer, such as those described in U.S. PatentApplication Publication No. 2012/0130011, herein incorporated byreference in its entirety. For example, the olefinic block copolymersmay be an elastomeric copolymer of polyethylene, sold under the tradename INFUSE by The Dow Chemical Company of Midland, Mich., (e.g., INFUSE9107). In one embodiment, the olefinic block copolymer is selected fromthe group consisting of INFUSE OBC 9000, INFUSE OBC 9007, INFUSE OBC9100, INFUSE OBC 9107, INFUSE OBC 9500, INFUSE OBC 9507, INFUSE OBC9530, INFUSE OBC 9807, INFUSE OBC 9817, and mixtures thereof.

In other particular examples, the base polymer may be any suchconfigured polymer such as those available from Kraton Polymers(Houston, Tex.), including but not limited to: Kraton MD6684, RP6684,FG190, FG1924, RP6670, 1901, 1901X, B 51-4, FG 120LX, FG 1652, FG 19, FG1900X, FG 1901, FG 1901X, FG 1901X951, FG 1921X, FG 1924, FG 1924X, FG1961X, G 1901, G 1901X, G 1901X2, G 1921, GRP 6627, KG 1901, M 1923, MB1000, RP 6509, RP 6510, RP 6543, RP 6562. In other embodiments, the basepolymer may be at least one of the following available from Asahi KaseiElastomer (Tokyo, Japan): Asahi M 1913, M 1943, and M 1953. In yet otherembodiments, the base polymer or thermoplastic rubber is a diblock or atriblock polymer sold under the trade name Septon (e.g., Septon 1020(diblock) or Septon 52006 (triblock)).

In other embodiments, the base polymer may further include at least oneof the following commercially available copolymers, includinghydrogenated styrenic block copolymers such as thepolystyrene-poly(ethylene-propylene) diblock copolymers available fromKraton Polymers as KRATON G1701 and G1702; thepolystyrene-poly(ethylene-butylene)-polystyrene triblock copolymersavailable from Kraton Polymers as KRATON G1641, G1650, G1651, G1654,G1657, G1726, G4609, G4610, GRP-6598, RP-6924, MD-6932M, MD-6933, andMD-6939; the polystyrene-poly(ethylene-butylene-styrene)-polystyrene(S-EB/S-S) triblock copolymers available from Kraton Polymers as KRATONRP-6935 and RP-6936, thepolystyrene-poly(ethylene-propylene)-polystyrene triblock copolymersavailable from Kraton Polymers as KRATON G1730; thepolystyrene-poly(ethylene-butylene)-polystyrene triblock copolymercomprising 67 wt % polystyrene available from Asahi Kasei Elastomer asTUFTEC H1043; the polystyrene-poly(ethylene-butylene)-polystyrenetriblock copolymer comprising 42 weight percent polystyrene availablefrom Asahi Kasei Elastomer as TUFTEC H1051; thepolystyrene-poly(butadiene-butylene)-polystyrene triblock copolymersavailable from Asahi Kasei Elastomer as TUFTEC P1000 and 2000; thepolystyrene-polybutadiene-poly(styrene-butadiene)-polybutadiene blockcopolymer available from Asahi Kasei Elastomer as S.O.E.-SS L601; thepolystyrene-poly(ethylene-butylene)-polystyrene triblock copolymercomprising about 60 wt % polystyrene available from Kuraray as SEPTON58104; the polystyrene-poly(ethylene-ethylene/propylene)-polystyrenetriblock copolymers available from Kuraray as SEPTON® 54044, 54055,54077, and 54099; and thepolystyrene-poly(ethylene-propylene)-polystyrene triblock copolymercomprising about 65 wt % polystyrene available from Kuraray as SEPTON®52104. Mixtures of two or more block copolymers may be used.Illustrative commercially available unhydrogenated block copolymersinclude the Kraton D series polymers, including KRATON D1101 and D1102,from Kraton Polymers, and the styrene-butadiene radial teleblockcopolymers available as, for example, K-RESIN KR01, KR03, KR05, and KR10sold by Chevron Phillips Chemical Company. In another embodiment, thestyrenic block copolymer is a mixture of high melt viscosity SEBS blockcopolymer and a functionalized SEBS block copolymer.

In another embodiment, the base polymer comprises maleic anhydridegrafted to the block copolymer. The maleated functional groups areexamples of functional groups configured for crosslinking during gelprocessing. These maleated base polymers are particularly configured forcrosslinking with extenders, di- and multi-amine crosslinkers, di- andmultifunctional epoxies, di- and multi-functional hydroxyl molecules(alcohols and polyols) as well as aluminum, titanium and otherorganometallic compounds. In some embodiments, the maleated base polymerincludes at least one functional group configured to chemicallycrosslink with a di- and multi-amine crosslinker.

For further example, the maleated functional groups of a maleicanhydride-modified SEBS or SEPS are configured for crosslinking. Notwishing to be bound by theory, but it is believed that chemicalcrosslinking of the SEBS or SEPS triblocks at the ethylene-butylene orethylene-propylene blocks further strengthens the gel structure. Thechemical crosslinking produced is capable of raising its softeningtemperature.

Methods of preparing maleated block copolymers are known in the art andmany such block copolymers are commercially available. For example,maleated block copolymers are disclosed in EP 0879832A1. Illustrativecommercially available maleic anhydride-modified SEBS are available fromKraton Polymers (Houston, Tex.) as KRATON FG1901 (SEBS polymer having apolystyrene content of about 30 wt % and maleic anhydride graftedcontent of about 1.4-2.0 wt %) and KRATON FG 1924 G (SEBS polymer withabout 13 wt % polystyrene and maleic anhydride grafted content of about0.7-1.3 wt %), and KRATON MD 6684 CS (SEBS polymer having a polystyrenecontent of about 30 wt % and maleation level of about 1.0 wt %), andKRATON MD 6670. Illustrative commercially available maleicanhydride-modified SEBS are available from Asahi Chemical Industry Co.,Ltd. (Tokyo, Japan) under the trade name M-1911(maleation level of about3.0 wt %), M-1913 (maleation level of about 2.0 wt %), and M-1943.

In one embodiment, the maleic anhydride modified SEBS is KRATONMD6684CS. In another embodiment, the maleic anhydride-modified SEBS isKRATON FG6684. In yet another embodiment, the maleic anhydride modifiedSEBS is selected from the group consisting of as KRATON FG1901, KRATONFG 1924 G, KRATON MD 6684 CS, and KRATON MD 6670. In another embodiment,the maleic anhydride-modified SEBS has a maleation level of betweenabout 1.0 wt % and about 3.0 wt %.

In certain embodiments, the base polymer comprises at least onefunctional group configured to chemically crosslink in the presence of afunctionalized extender or crosslinker, such as those described in U.S.patent application Ser. No. 13/955,243, filed Jul. 31, 2013, and hereinincorporated by reference. For example, the base polymer may havefunctional groups such as acyls, hydroxyls, sulfhydryls, amines,carboxyls, anhydrides, olefins, and carboxylic acids configured tochemically link in the presence of an extender or crosslinker.

In certain embodiments, the thermoplastic gel includes a functionalizedextender capable of forming a connection with the base polymer and“extending” the length of the base polymer. In certain embodiments, thefunctionalized extender comprises at least one functional group that iscompatible and willing to react with a functional group in the basepolymer or the crosslinker/coupling agent. In certain embodiments, thefunctionalized extender may be any compound that comprises a functionalsite that is capable of forming a connection to the base polymer or thecrosslinker/coupling agent. The functional group may be an olefin, forexample.

In some embodiments, the functionalized extender comprises an internalolefin. In other embodiments, the functionalized extender comprises aterminal double bond (a-olefin). In certain embodiments, thefunctionalized extender includes only one functional group. In someembodiments, the functionalized extender comprises a single, terminalolefin. Not wishing to be bound by theory, but it is believed that whenthe functionalized extender includes only one functional group permolecule (such as a terminal double bond), then a highly crosslinkedstructure can be prevented by the stoichiometry of the components, andthe resulting gel can be melt processed more readily. A functionalizedextender containing only one functional group can assist in locking theextender into the gel structure and prevent the extender from bleedingout as readily as similar gels made with non-functionalized(non-reactive) extenders.

In other embodiments, the functionalized extender comprises more thanone functional group. The functionalized extender may comprise acompound having more than one olefinic site, such as a butadiene. In oneparticular embodiment, the functionalized extender comprises acarboxy-terminated butadiene compound.

In certain embodiments, the extender can be locked into the gelstructure either by making it physically or chemically attracted to thepolymeric or functional portion of the base polymer, or by adding acrosslinker (or coupling agent) that connects the functionalizedextender to the base polymer. In a preferred embodiment, thefunctionalized extender is connected to the base polymer (eitherdirectly or through a coupling agent) in only one location per extendermolecule.

In some embodiments, the functionalized extender is selected from thegroup consisting of: polyisobutylene, unsaturated hydrocarbon oils,unsaturated paraffin, alkenes or olefins (mineral or synthetic),unsaturated naturals oils such as castor, linseed, soybean, peanut,esters or phthalate esters, polybutadiene, polyisoprene,poly(butadiene/styrene) copolymers, other liquid rubbers, and mixturesthereof. In one embodiment, the functionalized extender ispolyisobutylene (PIB).

In certain embodiments, the functionalized extender is a maleatedextender, such as maleated polyisobutylene or maleated polybutadiene. Inone particular embodiment, the functionalized extender is maleatedpolyisobutylene. In some embodiments, the extender compound is reactedwith maleic anhydride to form a maleated extender. In one particularexample, about 45 g of maleic anhydride is added to about 500 g ofheated polyisobutylene (TPC 595 from Texas Petrochemicals, Houston,Tex.), wherein the reaction is carried out at about 190° C. for about 6hours. The hot maleated polyisobutylene is then filtered through a 200mesh filter to remove any charred particles, and then put in sealedglass containers under dry nitrogen. The resulting composition wasapproximately 80% maleated as determined by the stoichiometry of theingredients and average molecular weight of the polyisobutylene. Otherfunctionalized extenders (including other polyisobutylene compositionssuch as Indopol® H100 polyisobutylene, INEOS Oligomers, League City,Tex., or Glissopal 1300 from BASF) may also be maleated using a similarprocedure.

In certain embodiments, the thermoplastic gel includes a crosslinker orcoupling agent that is capable of forming connections between the basepolymer chains, between the base polymer and functionalized extender, orbetween functionalized extenders. In certain embodiments, thecrosslinker comprises multiple (2 or more) functional groups that arecompatible and willing to react with the functional groups in the basepolymer or functionalized extender. In certain embodiments, thecrosslinker comprises between three and ten functional groups that arecapable of forming a connection point between three and ten basepolymers or functionalized extenders, such that the crosslinkerfunctions as a branching agent. In another embodiment, the crosslinkercomprises four functional groups that are capable of forming aconnection point between four different base polymers or functionalizedextenders.

Any crosslinker capable of reacting with the functionalized base polymerregions can be utilized, such as covalent bond crosslinking (covalentcrosslinkers) or ionic bond crosslinking (ionic crosslinkers).

In certain embodiments, the crosslinker is an ionic crosslinker, whichmay allow for improved re-melting or re-processing the gel by breakingor disassociating the bond at an elevated temperature. In certainembodiments, an ionic crosslinked gel may be re-melted or reprocessed byplacing the gel sample in a picture frame mold (in some cases, a moldthat is has dimensions of about 200 mm by about 200 mm by about 3 mmwith sheets of release paper or film on each side of the gel samples,wherein the total amount of gel placed in the mold is 60 g). Thematerial may then be pressed in a heated hydraulic press for about 2-3minutes (or until melted) at about 180° C. and about 10,000 pounds offorce. The sample may then be cooled to room temperature and removed.Samples of other shapes can be molded in a manner similar to injectionmolding plastic. In some embodiments, the re-melting/re-processingtemperatures may range between about 190° C. and about 230° C., and thepressures may range between about 300 psi and about 1,000 psi dependingon the size and geometry of the sample. Plastic injection moldingmachines, pressurized drum melters, and gear pumps may all be used tomelt gel and pressurize the gel to force it into the desired mold.

In some embodiments, the ionic crosslinker is a metal salt. Organicmetal salts may aid in coupling the (maleated) extender to the basepolymer molecules. In certain embodiments, the metal salt is a lithium,sodium, calcium, aluminum, or zinc organic metal salts. In oneembodiment, the ionic crosslinker is a calcium salt (such as Licomont®CaV 102).

In one embodiment, the ionic crosslinker is aluminum acetylacetonate. Infurther embodiments, the ionic crosslinker is selected from the groupconsisting of aluminum acetylacetonate, iron acetylacetonate, zincacetylacetonate, titanium acetylacetonate and zirconium acetylacetonate,and mixtures thereof. In one embodiment, the crosslinker is an aluminumsalt of acetic acid. For example, the crosslinker may be an aluminumtriacetate (Al(C₂H₃O₂)₃, aluminium diacetate, (HO(Al(C₂H₃O₂)₃), oraluminium monoacetate, ((HO)₂(Al(C₂H₃O₂)₃). In another embodiment, thecrosslinker is tetra(2-ethylhexyl)titanate.

In certain embodiments, the chemical crosslinking involves covalentcrosslinking (or a covalent crosslinker). Non-limiting examples ofcovalent crosslinkers include primary, secondary, or tertiary amines,epoxies, hydroxyl-terminated butadienes, polymeric di-isocynates, andmixtures thereof.

In other embodiments, the covalent crosslinker is an amine crosslinker.In further embodiments, the amine crosslinker is selected from the groupconsisting of an organic amine, an organic diamine, and an organicpolyamine. In other embodiments, the amine crosslinker is selected fromthe group consisting of ethylene diamine; 1,2- and 1,3-propylenediamine; 1,4-diaminobutane; 2,2-dimethylpropane diamine-(1,3);1,6-diaminohexane; 2,5-dimethylhexane diamine-(2,5);2,2,4-trimethylhexane diamine-(1,6); 1,8-diaminooctane;1,10-diaminodecane; 1,11-undecane diamine; 1,12-dodecane diamine;1-methyl-4-(aminoisopropyl)-cyclohexylamine-1;3-aminomethyl-3,5,5-trimethyl-cyclohexylamine-(1);1,2-bis-(aminomethyl)-cyclobutane; p-xylylene diamine; 1,2-and1,4-diaminocyclohexane; 1,2-; 1,4-; 1,5- and 1,8-diaminodecalin;1-methyl-4-aminoisopropyl-cyclohexylamine-1; 4,4′-diamino-dicyclohexyl;4,4′-diamino-dicyclohexyl methane;2,2′-(bis-4-amino-cyclohexyl)-propane;3,3′-dimethyl-4,4′-diamino-dicyclohexyl methane;1,2-bis-(4-aminocyclohexyl)-ethane;3,3′,5,5′-tetramethyl-bis-(4-aminocyclohexyl)-methane and -propane;1,4-bis-(2-aminoethyl)-benzene; benzidine; 4,4′-thiodianiline,dianisidine; 2,4-toluenediamine, diaminoditolylsulfone;2,6-diaminopyridine; 4- methoxy-6-methyl-m-phenylenediamine;diaminodiphenyl ether; 4,4′-bis(o-toluidine); o-phenylenediamine;o-phenylenediamine, methylenebis(o-chloroaniline);bis(3,4-diaminiophenyl)sulfone; diaminiodiphenylsulfone;4-chloro-o-phenylenediamine; m-aminobenzylamine; m-phenylenediamine;4,4′-C1-C6-dianiline such as 4,4′-methylenedianiline;aniline-formaldehyde resin; and trimethylene glycol di-p-aminobenzoateand mixtures thereof.

In further embodiments, the amine crosslinker is selected from the groupconsisting of bis-(2-aminoethyl)-amine, bis-(3-aminopropyl)-amine,bis-(4-aminobutyl)-amine and bis-(6-aminohexyl)-amine, and isomericmixtures of dipropylene triamine and dibutylene triamine. In yet furtherembodiments, the amine crosslinker is selected from the group consistingof diethanolamine, triethanolamine,N,N,N′,N′-[tetrakis(2-hydroxyethyl)ethylene diamine],N,N,-diethanolaniline hexamethylene diamine, tetramethylene diamine, anddodecane diamine and mixtures thereof.

In other embodiments, the covalent crosslinker is a polyol crosslinker.In further embodiments, the polyol crosslinker is selected from thegroup consisting of polyether-polyols, polyester-polyols, branchedderivatives of polyether-polyols (derived from, e.g., glycerin,sorbitol, xylitol, mannitol, glucosides, 1,3,5-trihydroxybenzene),branched derivatives of polyether-polyols (derived from, e.g., glycerin,sorbitol, xylitol, mannitol, glucosides, 1,3,5-trihydroxybenzene),orthophthalate-based polyols, ethylene glycol-based polyols, diethyleneglycol-based aromatic and aliphatic polyester-polyols. In furtherembodiments, the polyol crosslinker is selected from the groupconsisting of 1,2-propanediol, 1,3-propanediol. In other embodiments,the polyol crosslinker is selected from the group consisting ofpolycaprolactone diol, poly(propylene glycol), poly(ethylene glycol),poly(tetramethylene glycol), and polybutadiene diol and theirderivatives or copolymers.

Softener Oil

The gel compositions disclosed and made by methods disclosed herein maycomprise at least one softener oil composition. In particular, the gelmay include a softener oil comprising greater than 50 wt %, 60 wt %, 70wt %, or 80 wt %, and less than 99 wt %, 95 wt %, 90 wt %, or 85 wt % ofthe base composition. In other embodiments, the softener oil is betweenabout 51-99 wt %, about 60-95 wt %, or about 80-95 wt % of the basecomposition.

In certain embodiments, the softener oil is selected from the groupconsisting of: mineral oils, paraffin oil, naphthenic oil, aromaticoils, poly-alpha olefins (PAOs), or combinations thereof. In someembodiments, the softener oil is a mineral oil. In one particularembodiment, the softener oil is a white mineral oil, such as HYDROBRITE380 PO (Sonnebom). In other embodiments, the mineral oil is anepoxidized mineral oil.

In yet another embodiment, the softener oil is a paraffin oil. In otherembodiments, the softener oil is a naphthenic oil. In yet otherembodiments, the softener oil is an aromatic oil.

In some embodiments, the softener oil is a poly-alpha olefin (PAO) or alinear-alpha olefin. PAOs may comprise hydrogenated synthetichydrocarbon fluids used in a large number of automotive, electrical, andother industrial applications. DURASYN poly-alpha olefins are authorizedfor use as components of non-food articles and are considered non-toxic.In some embodiments, the PAO is a SYNFLUID® PAO, for example, a decenedimer, or a polydecene. DURASYN® 148 poly-alpha olefin is a fullysynthesized hydrogenated hydrocarbon base fluid produced from C12 linearalpha olefin feed stocks and available from INEOS Oligomers, Houston,Tex. In other embodiments, the PAO is selected from the group consistingof polypropylene, polybutene (e.g., polyisobutylene), didecene,polydecene, or combinations thereof.

In certain embodiments, the softener oil is a high molecular weight oilhaving a molecular weight greater than about 250 g/mol. In someembodiments, the high molecular weight oil has a molecular weightgreater than 250 g/mol, 400 g/mol, or 500 g/mol, and less than 2000g/mol, 1500 g/mol, 1200 g/mol, 1000 g/mol, 900 g/mol, 800 g/mol, 700g/mol or 600 g/mol. In some embodiments, the high molecular weight oilhas a molecular weight between 250 g/mol and 1500 g/mol, between 400g/mol and 900 g/mol, or between 500 g/mol and 800 g/mol.

The high molecular weight oil may be derived from any of the softeneroil compositions defined above, such as the mineral oils, paraffin oil,naphthenic oil, aromatic oils, poly-alpha olefins (PAOs), orcombinations thereof. The use of a high molecular weight oil may haveperceived disadvantages for use in the thermoplastic gel compositionsuch as (1) lower solubility of the base polymer in the oil, (2) higherbleed oil, or (3) increased melt viscosity. Nonetheless, the potentialnegative properties of the high molecular weight oil may be offset byadjusting the amount of base polymer content (e.g., diblock), mineralfiller content, and/or anti-tack agent content in the overall gelcomposition.

Fillers, Anti-Tack Agents, Stabilizers and Additional Additives

In certain embodiments, the thermoplastic gel composition may compriseadditional components. In one embodiment, the thermoplastic gelcomposition comprises at least one mineral filler. In anotherembodiment, the gel composition comprises an anti-tack or slip agent. Inother embodiments, the gel composition may include other additives suchas flame retardants, coloring agents, adhesion promoters, antioxidants,dispersants, flow improvers, plasticizers, toughening agents, andcombinations thereof.

Mineral Fillers

In one embodiment, the at least one additive is a mineral filler,wherein the filler is between about 0.1-50 wt % of the overallcomposition, about 5-40 wt % of the overall gel composition, or about15-30 wt % of the overall composition.

It has been discovered that use or blending of mineral fillers inthermoplastic gel compositions may improve moldability of the gel withreduced tackiness and improved thermal conductivity, while maintainingor even improving suitable sealing characteristics (e.g., low oil bleedout). It was also discovered that addition of a mineral filler mayreduce the gel composition's melt viscosity while maintain the gel'shardness characteristics (as the base polymer/thermoplastic rubbercontent can be decreased). Addition of the mineral filler may alsoreduce the material cost for the overall gel composition.

In certain embodiments, the mineral filler is selected from the groupconsisting of: talc, calcium carbonate, clay (e.g. Kaolin clay),wollastonite, silicates, glass (e.g., fiber, balls, hollow spheres), andcombinations thereof. In one particular example, the mineral filler is atalc. Such as a Luzenac available from Imerys. Talc may be blended withthe base composition as opposed to applying it just to the surface ofthe composition.

Anti-Tack Agents

In certain embodiments, the gel composition comprises an anti-tack orslip agent. Such anti-tack agents may be added to the base polymer toreduce the gel composition's tackiness or even achieve a certain levelof surface lubrication. In some embodiments, polyethylene orpolypropylene may be used as the anti-tack agent. In other embodiments,the anti-tack agent is a silicone, silane, or siloxane compound, or acopolymer thereof, such as an organo-modified siloxane. It has beendiscovered that use of certain anti-tack agents (such as silicone,silane, or siloxane compounds) will allow for an increased amount ofbase polymer (e.g., diblock) in the overall gel composition, which mayprovide improved oil retention of the gel. In other words, the use ofcertain anti-tack agents may provide improved oil retention andtackiness characteristics while maintaining other gel characteristics.In some embodiments, the anti-tack agent is between about 0.1 and 10 wt% of the overall composition, and in other embodiments between about 0.2and 5 wt % of the overall composition. Tack reducing agents that seem tobe most effective are those that are insoluble in the hydrocarbonextender oil such as silicone oligomers based on polydimethyl siloxaneor phenyl methyl polysiloxane.

Stabilizers

The gel compositions disclosed and made by methods disclosed herein maycomprise at least one stabilizer. In particular, the gel may include astabilizer comprising between about 0.1-5 wt % or about 0.5-3 wt %, ofthe overall composition.

In some embodiments, the stabilizer is selected from the groupconsisting of antioxidants, acid-scavengers, light and UVabsorbers/stabilizers, heat stabilizers, metal deactivators, freeradical scavengers, carbon black, antifungal agents, and mixturesthereof. The stabilizer may be selected from the group consisting of:hindered phenols (e.g., Irganox™ 1076, commercially available fromCiba-Geigy Corp., Tarrytown, N.Y.); phosphites (e.g., Irgafos™ 168,commercially available from Ciba-Geigy Corp.); metal deactivators (e.g.,Irganox™ D1024, commercially available from Ciba-Geigy Corp.); sulfides(e.g., Cyanox LTDP, commercially available from American Cyanamid Co.,Wayne, N.J.); light stabilizers (e.g., Cyasorb UV-531, commerciallyavailable from American Cyanamid Co.); phosphorous containing organiccompounds (e.g., Fyrol PCF and Phosflex 390, both commercially availablefrom Akzo Nobel Chemicals Inc. of Dobbs Ferry, N.Y.); acid scavengers(e.g., DHT-4A, commercially available from Kyowa Chemical Industry Co.Ltd through Mitsui & Co. of Cleveland, Ohio, and hydrotalcite); andmixtures thereof.

In certain embodiments, the gel composition comprises at least onestabilizer. In particular, the gel may include a stabilizer comprisingbetween about 0.1-5 wt %, about 0.5-3 wt %, or about 1-2 wt % of theoverall composition.

In some embodiments, the stabilizer is selected from the groupconsisting of antioxidants, acid-scavengers, light and UVabsorbers/stabilizers, heat stabilizers, metal deactivators, freeradical scavengers, carbon black, antifungal agents, and mixturesthereof. In some embodiments, the stabilizer is a hindered phenolicantioxidant. The stabilizer may be selected from the group consistingof: hindered phenols (e.g., Irganox™ 1076, commercially available fromCiba-Geigy Corp., Tarrytown, N.Y.); phosphites (e.g., Irgafos™ 168,commercially available from Ciba-Geigy Corp.); metal deactivators (e.g.,Irganox™ D1024, commercially available from Ciba-Geigy Corp.); sulfides(e.g., Cyanox LTDP, commercially available from American Cyanamid Co.,Wayne, N.J.; light stabilizers (e.g., Cyasorb UV-531, commerciallyavailable from American Cyanamid Co.); phosphorous containing organiccompounds (e.g., Fyrol PCF and Phosflex 390, both commercially availablefrom Akzo Nobel Chemicals Inc. of Dobbs Ferry, N.Y.); acid scavengers(e.g., DHT-4A, commercially available from Kyowa Chemical Industry Co.Ltd through Mitsui & Co. of Cleveland, Ohio, and hydrotalcite); andmixtures thereof.

Additional Additives

In another embodiment, the gel comprises a toughening agent that mayimprove the ability for the composition to deform without breaking. Insome embodiments, the toughening agent may allow the composition to bestrained to approximately 800%, 1,000%, or 1,200% of its original sizebefore breaking. In certain embodiments, the toughening agent is a fumedsilica. In certain embodiments, the fumed silica is between about 0.1-30wt % of the overall composition, about 1-25 wt % of the overallcomposition, or about 5-20 wt % of the overall composition. Onenon-limiting example of a fumed silica that may be used in the gelcomposition is AEROSIL® R9200 modified, hydrophobic fumed silica,available from Evonik Degussa Corp. (Parsippany, N.J., USA).

In some embodiments, the compositions disclosed and made by methodsdisclosed herein comprise a flame retardant. The flame retardant may bea halogenated paraffin (e.g., Bromoklor 50, commercially available fromFerro Corp., Hammond, Ind.), a metal hydride, calcium carbonate, zincoxide, or a siloxane (such as Casico™ available from Borealis AG,Vienna, Austria). In some embodiments, the flame retardant is betweenabout 0.1 and 25 wt % of the overall composition, between about 0.1 and5 wt % of the overall composition, between about 0.1 and 2 wt % of theoverall composition, or between about 0.1 and 1 wt % of the overallcomposition. In one embodiment, the flame retardant comprises about 20wt % of the overall gel composition.

Other suitable additives include colorants, biocides, tackifiers, andthe like, described in “Additives for Plastics, Edition 1” published byD.A.T.A., Inc. and The International Plastics Selector, Inc., San Diego,Calif.

In certain embodiments, the additional additives may include at leastone material selected from the group consisting of Dynasylan 40, PDM1922, Songnox 1024, Kingnox 76, DHT-4A, Kingsorb, pigment, and mixturesthereof. In some embodiments, the additives comprise between about 0.1and 25 wt % of the overall composition, between about 0.1 and 5 wt % ofthe overall composition, between about 0.1 and 2 wt % of the overallcomposition, or between about 0.1 and 1 wt % of the overall composition.

Uses and Properties of the Thermoplastic Gel, and Testing Methods

The gels described herein may be used in a number of end uses due totheir improved properties, such as improved behavior in mechanicalstresses (e.g., vibration and shock) or ability to seal uneven orcomplicated structures (due to the ability to flow and adapt to the areaof the structure). In certain embodiments, the gel may be used in aninterconnect, cover, or closure system. In particular, the gel may beused in a fiber optic closure, electrical sealant, or electricalclosure. In some embodiments, the gels are used as gel wraps,clamshells, or gel caps. In further embodiments, the gels are used inthe inside of a residence. In other embodiments, the gels are usedoutside of a residence. Use of the gel within a closure or interconnectsystem may allow for a reduction in the number of components, framesize, or cost over other sealing mechanisms.

With regards to use as a sealant, the gels described herein tend toexhibit a unique stress-strain dynamic, as further described below. Withan increase in strain beyond the point of the elastic (linear) portionof the curve, the gel exhibits a somewhat exponential increase in stressprior to the failure point. In other words, the gel tends to become evenstiffer with an increase in strain or pressure on the gel as itapproaches its failure point. In certain examples, such as within aclosure, the gel is stiff at the higher strain points near the ends ofthe closure, keeping the softer gel composition within the closure fromextruding out of the closure.

In certain embodiments, the gel is used as a dampener. In certainembodiments, the gel is used as a flame retardant sealant. In oneembodiment, the gel comprises a flame retardant additive (e.g., zincoxide) in order to function as a flame retardant sealant.

In certain embodiments, the gel is used in a closure or enclosuresystem. In certain embodiments, the closure system comprises a housing,a cable, and a gel.

In some embodiments, a closure, enclosure or interconnect system isprovided comprising a housing, a cable, and a thermoplastic gelcomprising a base composition consisting of a thermoplastic rubber and asoftener oil; and at least one additive selected from the groupconsisting of a mineral filler, an anti-tack agent, and mixturesthereof, wherein the base composition and at least one additive definean overall composition, and wherein the gel has a hardness between 15Shore 000 and 65 Shore 000.

In some embodiments, a closure, enclosure or interconnect system isprovided comprising a housing, a cable, and a thermoplastic gelcomprising a base composition consisting of a thermoplastic rubber and asoftener oil, wherein the softener oil is a high molecular weight oilhaving a molecular weight greater than 250 g/mol, and wherein the gelhas a hardness between 15 Shore 000 and 65 Shore 000.

In some embodiments, the system further comprises a connector, and, insome instances, a receptacle or port, therein forming an interconnectsystem. The interconnect system may comprise a mini input/outputconnector, data connector, power connector, fiber optic connector, orcombination thereof. For example, the interconnect system may comprise aRJ-45 connector system. Non-limiting examples of interconnect systemsand components are displayed in FIGS. 1, 2, 3, 4 a, 4 b, 5 a, and 5 b.

The gel may be used to create a seal formed by displacement. In otherembodiments, the gel may be used to create a seal having radialfunctionality, axial functionality, or a combination thereof. In yetother embodiments, the gel may be used to create a seal formed bydisplacement and having radial and/or axial functionality.

FIGS. 1, 2, and 3 provide non-limiting examples of radial and axialfunctionality. FIG. 1 displays an example of a connection hub havingmultiple connection receptacles or ports for the cables 16 within thehousings 14 to be connected. FIG. 1 displays both radial connectionports 10 and axial connection ports 12. FIG. 2 displays a connector 26;housing 18, 28; and cable 16 assembly with radial sealing 22. FIG. 3displays a connector 26; housing 32, 34; and cable 16 assembly withaxial sealing 30, wherein the seal follows the surface of the axial port12 (as shown in FIG. 1). In certain embodiments, the housing may have aknob 20 that may be pushed inward to engage the latch 24 on theconnector 26, allowing the connector to be removed from the port.

In certain embodiments, the gel may be used to create a seal in ahousing assembly having multiple parts. For example, in one embodimentthe gel may be used in a straight two-piece housing assembly, as shownin FIGS. 4a and 4b . Similar to FIG. 3, FIGS. 4a and 4b display atwo-piece housing 32, 34, having axial sealing 30, wherein the sealfollows the surface of the axial port 12 (as shown in FIG. 1). Incertain embodiments, the housing may have a knob 20 that may be pushedinward to engage the latch 24 (as shown in FIG. 3) on the connector 26(as shown in FIG. 3), allowing the connector to be removed from theport.

In another embodiment, the gel may be used in an angled two-piecehousing assembly, as shown in FIGS. 5a and 5b . FIGS. 5a and 5b displaya connector 26; angled two-piece housing 36, 38; and cable 16 assemblywith axial sealing 30, wherein the seal follows the surface of the axialport 12 (as shown in FIG. 1). In certain embodiments, the housing mayhave a knob 20 that may be pushed inward to engage the latch 24 on theconnector 26, allowing the connector to be removed from the port.

The gel may be sealed around the cable 16 by sliding a smaller diametergel formation over the cable to create a seal through interference. Inother embodiments, the seal may be created by molding the gel around theinside of the housing components and then snapping the housing, gel, andcable into place.

In certain embodiments, the gel is used as a sealant in atelecommunications enclosure. Non-limiting examples oftelecommunications enclosures are shown in FIGS. 6-10.

FIGS. 6-8 show a telecommunications enclosure 120 suitable for using asealing material in accordance with the principles of the presentdisclosure. The enclosure 120 includes a housing 122 having an end 124defining a sealing unit opening 126. The sealing unit opening 126 isdefined by a base 127 of the enclosure 120. The base 127 has a hollowsleeve-like configuration. As shown in FIGS. 6 and 8, a dome-style cover129 is secured to the base 127 by a channel clamp 125. The enclosure 120also includes a sealing unit 128 (see FIGS. 8-10) that fits within thesealing unit opening 126. The sealing unit 128 includes a sealantarrangement 132 (see FIGS. 9 and 10) defining a plurality of cable ports130. The sealant arrangement can include a material having stress-straincharacteristics in accordance with the principles of the presentdisclosure. In certain embodiments, the sealant arrangement can includea gel of the type disclosed herein. When pressurized, the sealantarrangement 132 is configured for providing seals about structures(e.g., cables, plugs, etc.) routed though the cable ports 130 and isalso configured for providing a peripheral seal with the housing 122.The enclosure 120 further includes an actuation arrangement 131 (seeFIG. 9) for pressurizing the sealant arrangement 132 within the sealingunit opening 126. In other embodiments, the housing can be an enclosure(e.g., an aerial enclosure) having a pass-through configuration withsealing units located at opposite ends of the enclosure. In certainembodiments, a frame supporting optical components (e.g., opticalsplices, optical splitters, optical splice trays, optical splittertrays, fiber management trays, passive optical splitters, wavelengthdivision multi-plexers, etc.) can be mounted within the enclosure 120.

Referring to FIG. 9, the actuation arrangement 131 includes inner andouter pressurization structures 160, 162 (e.g., plates, members, bodies,etc.). The sealant arrangement 132 is positioned between the inner andouter pressurization structures 160, 162. The actuation arrangement 131also includes a threaded shaft 149 that extends between the inner andouter pressurization structures 160, 162 and a nut 151 that is threadedon the threaded shaft 149. The actuation arrangement further includes aspring 152 for transferring a seal pressurization force to the sealantarrangement 132. The spring 152 is captured between the nut 151 and theouter pressurization structure 162. An extension 153 (e.g., a wrench orother tool) is used to turn the nut 151 a first rotational direction(e.g., clockwise) on the threaded shaft 149 causing the spring 152 to becompressed between the nut 151 and the outer pressurization structure.As the spring 152 is compressed, the threaded shaft 149 is tensioned andthe inner and outer pressurization structures 160, 162 are drawntogether. As the inner and outer pressurizations structures 160, 162 aredrawn together, the sealant arrangement 132 is pressurized between thepressurization structures 160, 162 causing the sealant arrangement 132to flow/deform to fill voids within the sealing unit opening 126, toform the peripheral seal with the housing 122, and to form seals aroundany cables or inserts positioned within cable ports 130. Thus, when theactuation arrangement 131 is actuated, the first and secondpressurization plates 60, 62 are spring biased toward one another suchthat spring pressure is applied through the sealant arrangement 132 forpressurizing the sealant arrangement 132 to maintain effective sealingover an extended period of time. In other embodiments, differentactuation configurations can be used. The sealant arrangement 132 can bede-pressurized by turning the nut 151 a second rotational direction(e.g., counterclockwise) on the shaft 149 to decompress the spring 152.

Referring to FIGS. 9 and 10, two cables 180 are shown passing throughthe cable ports 130 while the remainder of the cable ports 130 are shownblocked with plugs. The cables 180 include outer jackets 182 containinga plurality of buffer tubes 184. A plurality of optical fibers 186 arecontained in each of the buffer tubes 184. The cables 180 also includecenter strength members 188 (e.g., fiberglass reinforced epoxy rods)that provide the cables with tensile and compressive reinforcement. Inother embodiments, reinforcing members in the form aramid yarns or otherreinforcing structures can be used. In certain embodiments, the cables180 can be LSZH cables. When pressurized, the sealant arrangement 132contacts the outer jackets 182 and forms cable seals 190 aroundperipheries of the cable jackets 182. When pressurized, the sealantarrangement 132 also contacts an interior of the base 127 to form aperipheral seal 192 with the base 127. Cables having alternativeconstructions (e.g., flat drop cables, cables without buffer tubes,cables without center strength members, etc.) can also be used.

In certain embodiments, the gel has measurable properties. Gelproperties may be measured under the International TelecommunicationUnion standardization sector (ITU-T), and Series L.13, in particular.Various properties such as pressure loss, tightness, visual appearance,etc. are discussed in this standard.

Additionally, the gel may have a hardness in the range of about 15 toabout 65 Shore 000 Hardness, as measured according to methods known inthe art. In certain embodiments, the gel exhibits a hardness in therange of 30 to 45 Shore 000 Hardness. In certain embodiments, the shorehardness gauge is measured according to ISO868 or ASTM D2240. In otherembodiments, hardness can be measured on a texture analyzer. Forexample, a LFRA Texture Analyzer-Brookfield may include a probe assemblyfixed to a motor driven, bi-directional load cell. In such a system, theprobe is driven vertically into the sample at a pre-set speed and to apre-set depth. The hardness is the amount of force needed to push theprobe into the test sample. In other embodiments, the gel has a hardnessin the range of about 24 to about 53 Shore 000, or about 80 to about 300g. In yet other embodiments, the gel has a hardness in the range ofabout 37 to about 45 Shore 000, or about 160 to about 220 g. In yetother embodiments, the gel has a hardness in the range of about 38 toabout 42 Shore 000, or about 170 to about 200 g. In other embodiments,the gel has a hardness in the range of 32 to 41 Shore 000. In yet otherembodiments, the gel has a hardness in the range of 37 to 42 Shore 000.

In some embodiments, stress relaxation of the gel is determined. The gelis compressed with a certain strain or deformation (e.g., in certainembodiments, to 50% of its original size). This causes a certain stressin the material. The stress is now reduced because the material relaxes.In certain embodiments, the stress relaxation of the gel has a possiblerange between 12 and 35% when subjected to a tensile strain ordeformation of about 50% of the gel's original size, wherein the stressrelaxation is measured after a one minute hold time at 50% strain. Inother embodiments, the stress relaxation of the gel is between 20% and30% when subjected to a tensile strain of about 50%. A higher stressrelaxation indicates that once a gel is installed in a closure, the gelwill require less stress in order for it to seal.

In certain embodiments, the gel composition is used to prepare athermoplastic gel exhibiting less than about 10% bleed out over a periodof time when the gel is under compression of 50 kPa (0.5 atm) or 120 kPa(1.2 atm) at 60° C. In some embodiments, the gel exhibits less thanabout 15% oil bleed out over a period of time when the gel is undercompression of 120 kPa (1.2 atm) at 70° C. The weight of the gel sampleis recorded before and after the pressure has been applied. In certainembodiments, oil bleed out is measured on a wire mesh, wherein the oilloss may exit the gel through the mesh. Typically, gel samples should beabout 3 mm ±0.5 mm thick and have a diameter of about 14 mm ±0.5 mm, andthree samples should be tested from each gel. The gel sample is placedinto a cylindrical hole/tube resting on a fine and rough screen, whichgives enough support to hold the gel but in the meantime allows the oilto separate from the gel. Pressure is applied to the gel by placing aweight on top of a piston (which prevents the gel from creeping out ofthe hole). Typically, approximately 50 kPa (0.5 atm) or 120 kPa (1.2atm) of pressure is placed on the gel sample. Then, the sample is placedin an oven at about 60° C. After about 24 hours, the sample is removedfrom the oven to clean the surface oil and weigh the gel. The sample isthen returned to the oven. Weight measurements are taken every 24 hoursuntil stabilization has occurred (e.g., when 5 weight measurements areconstant).

In some embodiments, the gel has less than 8%, 6%, 4%, or 2% oil bleedout over the period of time. In certain embodiments, the oil loss ismeasured at 200 hours, 400 hours, 600 hours, 800 hours, 1,000 hours,1,200 hours, or 1,440 hours (60 days).

In certain embodiments, the gel has less oil bleed out in comparison toa thermoplastic gel over the same period of time at 50 kPa (0.5 atm) or120 kPa (1.2 atm) at 60° C. In some embodiments, the gel has less than20%, 30%, 40%, 50%, or 60% of the oil bleed out of a similar,traditional thermoplastic gel at 200 hours, 400 hours, 600 hours, 800hours, 1,000 hours, 1,200 hours, 1,440 hours (60 days), 2,000 hours, or3,000 hours.

In certain embodiments, the thermoplastic gel has less oil bleed out incomparison to a conventinalthermoplastic gel over the same period oftime at 50 kPa (0.5 atm) or 120 kPa (1.2 atm) at 70° C. In someembodiments, the gel has less than 20%, 30%, 40%, 50%, or 60% of the oilbleed out of a similar, traditional thermoplastic gel at 200 hours, 400hours, 600 hours, 800 hours, 1,000 hours, 1,200 hours, 1,440 hours (60days), 2,000 hours, or 3,000 hours.

In some embodiments, the thermoplastic gel exhibits one or more of thefollowing properties: a) a Shore 000 hardness between 30 and 45; b) astress relaxation between 10% and 35% when the gel is subjected to adeformation of 50% of its original size; c) less than 20% oil bleed outafter being under compression of 1.2 atm for 60 days at 70° C.

EXAMPLES

A variety of thermoplastic gels were made and tested as discussed below.

Example 1 High Molecular Weight Softener Oil

A thermoplastic gel was made using the following formula of Table 1.

TABLE 1 Thermoplastic gel formulation. Component Weight PercentFunctionalized extender 40.0-90.0 Synthetic hydrocarbon base fluid  0-40.0 Polydimethyl siloxane fluid  0-3.5 Hindered phenol stabilizer0.2-1.5 Maleated SEBS, maximum functionality 1.15% by  5.0-20.0 weightMaleated SEBS, maximum functionality 2.0% by  0-8.0 weight Fumed silica 0-5.0 Metal Acetyl Acetonate 0.5-2.5

400 g of above composition was blended in a laboratory planetary mixerfor 30 minutes at 210° C. The metal acetyl acetonate may be aluminumacetyl acetonate, zinc acetyl acetonate, iron acetyl acetonate, or anyother acetyl acetonate, such as chromium acetyl acetonate, zirconiumacetyl acetonate, and any combination of acetyl acetonates. Theresulting mixture when cooled formed a gel material.

Test samples of the mixture were prepared using a hot press by placing40 g of the mixture in a 3mm thick by 200 mm square picture frame moldfor 10 minutes at 10,000 Newtons of force. The plaque formed was used todetermine the following properties. The hardness of the gel wasapproximately 120g using a 6.35 mm semispherical probe inserted to adepth of 4mm in a 30 mm thick s gel sample at a rate of 2 mm/min. Theone minute stress relaxation value was 26%. The mechanical propertieswere average elongation to failure of 1,300%, and stress to failure of0.95 MPa measured on rings of 25mm diameter, 3 mm thick X 4 mm wideusing a universal test machine.

Example 2 Talc Filler

A thermoplastic gel was made using the formula according to Table 2:

TABLE 2 Thermoplastic gel formulation with talc filler Component WeightPercent Synthetic hydrocarbon base fluid 40.0-88.0  Hindered phenolicantioxidant 0.2-1.5  UV absorber 0.1-0.75 Hydrocarbon resin  0-15.0 SEBStriblock copolymer 4.0-20.0 SEP diblock copolymer 3.0-10.0 Talc 5.0-30.0

400g of above composition was blended in a laboratory planetary mixerfor 30 minutes at 210° C. The resulting mixture when cooled formed a gelmaterial. Samples were prepared and tested as described in Example 1.The results were 65 g hardness, 28% stress relaxation, elongation tofailure 1500% and strength of 0.2 MPa.

Examples 3-14 Additional Thermoplastic Gels

Additional thermoplastic gels were prepared from the compositions inTables 3 and 4 and tested as described in Example 1.

TABLE 3 Additional Thermoplastic Gel Compositions Comparative IngredientExample 3 Example 4 Example 5 Example 6 Example 7 Example 8 Synthetic30.00 20.00 74.50 73.60 Hydrocarbon Maleated PIB 0.00 44.50 74.50 53.00White Mineral Oil 77.20 Triblock copolymer 15.00 15.00 18.00 Diblockcopolymer 6.00 7.00 5.50 8.00 7.00 Maleated triblock 19.50 11.50 15.50copolymer Hindered phenol 1.20 1.00 1.00 1.00 1.40 1.40 stabilizer UVAbsorber 0.50 Polydimethyl 2.00 3.00 2.00 1.00 siloxane fluid Fumedsilica 2.00 2.00 2.00 Talc Metal acetyl 1.00 1.00 1.00 acetonate CalciumOxide Black pigment color concentrate UMB blue pigment 0.10 0.10 0.00TOTAL 100.00 100.00 100.00 100.00 100.00 100.00

TABLE 4 Additional Thermoplastic Gel Compositions Example ExampleExample Example Example Ingredient Example 9 10 11 12 13 14 Synthetic68.60 78.60 Hydrocarbon Maleated PIB White Mineral Oil 55.90 52.90 74.6060.20 Triblock copolymer 20.00 8.00 8.00 14.70 11.40 14.00 Diblockcopolymer 10.00 4.50 6.50 8.10 5.10 6.00 Maleated triblock copolymerHindered phenol 1.40 1.05 1.05 1.05 1.20 1.40 stabilizer UV Absorber0.35 0.35 0.35 0.40 Polydimethyl siloxane 1.00 1.00 1.00 fluid Fumedsilica Talc 30.00 30.00 20.00 Metal acetyl acetonate Calcium Oxide 0.50Black pigment color 0.20 0.20 0.20 0.20 concentrate UMB blue pigment0.00 TOTAL 100.00 100.00 100.00 100.00 100.00 100.00

Samples were prepared from the compositions of Examples 3-14 and testedas described in Example 1. Properties of thermoplastic gels of Examples3-14 are shown in Table 5.

TABLE 5 Thermoplastic Gel Properties. Oil bleed Stress out at Hardnessrelaxation 120 kPa, Tensile Elongation (Shore (%) (60 s 70° C. (%, #Strength to Break Example 000) value) days) (MPa) (%) 3 34 24 25%, 300.9 1800 days 4 43 24 NT 0.54 1000 5 44 28 NT 0.55 1050 6 41 30 NT 0.41150 7 32 21 NT 1.3 2300 8 35 23 8.8%, 33 1 1600 days 9 39 13 4.1%, 260.41 1400 days 10 27 23 16.8%, 62 0.24 1000 days 11 41 34 13.7%, 62 0.271100 days 12 38 28 8.4%, 62 0.28 1400 days 13 42 26 NT 0.54 1580 14 34NT 13.7%, NT NT 33 days NT = not tested

The gel samples exhibited a range of Shore 000 hardness of from 32 to44; and a range of stress relaxation (60 s value) of from 13-28%; atensile strength in a range from 0.41 to 1 MPa; and elongation to Break(%) in a range from 1000-2300%.

Example 3 comparative conventional thermoplastic gel example exhibited25 wt % oil bleed out under 120 kPa at 70° C. In contrast, examples 8,9, prepared from compositions comprising a synthetic hydrocarbon highmolecular weight softener oil, each exhibited less than 10 wt % oilbleed out under 120 kPa at 70° C. over a period of at least 26 days,while retaining favorable gel properties of hardness (Shore 000), stressrelaxation, tensile strength and elongation to break.

Examples 10 and 11, comprising talc, exhibited less than 20 wt %, orless than 15 wt % oil bleed out, respectively, over a period of 60 daysunder compression of 1.2 atm at 70° C. Examples 11 and 12, comprisinganti-tack agent polydimethyl siloxane exhibited less than 15 wt % oilbleed out after 60 days under compression of 1.2 atm at 70° C. Example12, comprising anti-tack agent polydimethyl siloxane fluid, exhibitedless than 10 wt % oil bleed out after 60 days under compression of 1.2atm at 70° C.

Example 15 Thermoplastic Gel Formulation

Thermoplastic gels were made from compositions according to Table 7.

TABLE 7 Thermoplastic Gel Formulation Component Weight Percent Softeneroil 50-80 Triblock copolymer  5-20 Diblock copolymer  3-12 Hinderedphenolic antioxidant 0.2-1.5 UV absorber   0-0.75 Polydimethyl siloxanefluid 0-5 Talc  0-40 Pigment 0-1

Thermoplastic gels were prepared employing the formulation of Table 7.The resulting mixtures when cooled formed gel materials and were testedaccording to Example 1. In the composition of Table 7, when both thepolydimethyl siloxane fluid and talc were absent, the softener oil was ahigh molecular weight synthetic hydrocarbon. In the presence of one orboth of the polydimethyl siloxane fluid and talc, the softener oil waseither synthetic hydrocarbon or white mineral oil. Samples were preparedand tested as described in Example 1. The results were hardness (Shore000) 35-(Shore 000) 41; 13-28% stress relaxation (60 s value);elongation to break 1000%-1600%; and tensile strength of 0.24-1 MPa.

Thermoplastic gels prepared according to the Formulation of Table 7exhibited less than 20 wt % oil bleed out, more typically less than 15wt %, or less than 10 wt % over a testing period of at least 26 daysunder 120 kPa at 70° C.

Example 16 Thermoplastic Gel-Oil Bleed Out

Selected thermoplastic gels of the Examples were tested over a period of33 days for oil bleed out as follows. The weight of the gel sample wasrecorded before and after the pressure was been applied. Oil bleed outwas measured on a wire mesh, wherein the oil loss may exit the gelthrough the mesh. Gel samples were prepared as described in Examples 1and 3 to a dimension of about 3 mm±0.5 mm thick with a diameter of about14 mm±0.5 mm, and three samples were tested from each gel. The gelsample was placed into a cylindrical hole/tube resting on a fine andrough screen, which gave enough support to hold the gel, but allowed theoil to separate from the gel. Pressure was applied to the gel by placinga weight on top of a piston (which prevents the gel from creeping out ofthe hole); 120 kPa (1.2 atm) of pressure was placed on the gel sample.Then, the sample is placed in an oven at about 70° C. After about aperiod of time, the sample is removed from the oven to clean the surfaceoil and weigh the gel. The sample was then returned to the oven. Weightmeasurements were taken at selected intervals of 0, 1, 4, 5, 6, 7, 8,11, 12, 19, 20, 21, 25, 26, 28, and/or 33 days. Extender weight loss (%)vs. days of 120 kPa pressure at 70° C. was plotted as shown in FIG. 11.Surprisingly, the inventive thermoplastic gels of Examples 8, 9 and 14each exhibited less than 15 wt % oil bleed out over the testing periodunder 120 kPa at 70° C. In contrast, the comparative thermoplastic gelof Example 3 without a mineral filler, an anti-tack agent or a highmolecular weight synthetic hydrocarbon softener oil, exhibited about 25wt % oil bleed out under the same conditions over a period of 28 days.Examples 8 and 9 exhibited less than 10% oil bleed out over a period of26 days under 120 kPa at 70° C. Example 9 exhibited less than 5% oilbleed out over a period of 26 days under 120 kPa at 70° C.

Although examples have been described herein, it should be appreciatedthat any subsequent arrangement designed to achieve the same or similarpurpose may be substituted for the specific examples shown. Thisdisclosure is intended to cover any and all subsequent adaptations orvariations of various examples. Combinations of the above examples, andother examples not specifically described herein, may be apparent tothose of skill in the art upon reviewing the description.

The Abstract is provided with the understanding that it will not be usedto interpret or limit the scope or meaning of the claims. In addition,in the foregoing Detailed Description, various features may be groupedtogether or described in a single example for the purpose ofstreamlining the disclosure. This disclosure is not to be interpreted asreflecting an intention that the claimed examples require more featuresthan are expressly recited in each claim. Rather, as the followingclaims reflect, inventive subject matter may be directed to less thanall of the features of any of the disclosed examples. Thus, thefollowing claims are incorporated into the Detailed Description, witheach claim standing on its own as defining separately claimed subjectmatter.

The above disclosed subject matter is to be considered illustrative, andnot restrictive, and the appended claims are intended to cover all suchmodifications, enhancements, and other examples, which fall within thetrue spirit and scope of the description. Thus, to the maximum extentallowed by law, the scope is to be determined by the broadestpermissible interpretation of the following claims and theirequivalents, and shall not be restricted or limited by the foregoingdetailed description

1.-21. (canceled)
 22. A thermoplastic gel comprising: a base compositionconsisting of a thermoplastic rubber and a softener oil, wherein thesoftener oil is a high molecular weight oil having a molecular weightgreater than 250 g/mol, and wherein the gel has a hardness between 15Shore OOO and 65 Shore OOO.
 23. The gel of claim 22, wherein the gelexhibits less than 10% oil bleed out after being under compression of1.2 atm for 26 days at 70° C.
 24. The gel of claim 22, wherein the highmolecular weight oil is derived from one of the following: a mineraloil, a paraffin oil, a naphthenic oil, an aromatic oil, a poly-alphaolefin, or a combination thereof.
 25. The gel of claim 22, wherein thethermoplastic rubber comprises a styrenic triblock copolymer.
 26. Thegel of claim 25, wherein the styrenic triblock copolymer is selectedfrom the group consisting of a styrene-ethylene/butylene-styrene and astyrene-ethylene/propylene-styrene copolymer.
 27. The gel of claim 22,wherein the thermoplastic gel further comprises a mineral filler,wherein the mineral filler is between 0.1 wt % and 50 wt % of theoverall composition.
 28. The gel of claim 27, wherein the mineral filleris selected from the group consisting of talc, calcium carbonate, clay,wollastonite, silicates, glass, and combinations thereof. 29.-30.(canceled)
 31. The gel of claim 22, wherein the thermoplastic gelfurther comprises an anti-tack agent, and wherein the anti-tack agent isbetween 0.1 wt % and 10 wt % of the overall composition.
 32. The gel ofclaim 31, wherein the anti-tack agent is selected from the groupconsisting of a silicone, silane, siloxane, or copolymer thereof. 33.(canceled)
 34. The gel of claim 22, wherein the thermoplastic rubbercomprises: (a) a base polymer having at least one functional groupcapable of crosslinking, (b) a functionalized extender, and (c) anoptional crosslinker having multiple functional groups that arecompatible and willing to react with the functional groups in the basepolymer or the functionalized extender. 35.-38. (canceled)
 39. The gelof claim 22 further comprising an additive selected from the groupconsisting of: flame retardants, coloring agents, adhesion promoters,stabilizers, dispersants, flow improvers, plasticizers, tougheningagents, and combinations thereof. 40.-62. (canceled)
 63. A method ofmaking a thermoplastic gel comprising mixing a base compositionconsisting of a thermoplastic rubber and a softener oil, wherein thesoftener oil is a high molecular weight oil having a molecular weightgreater than 250 g/mol, optionally with at least one additional additiveselected from the group consisting of a mineral filler, an anti-tackagent, a stabilizer, and mixtures thereof, to form an overallcomposition, and providing heat to the overall composition to form thethermoplastic gel, wherein the gel has a hardness between 15 Shore OOOand 65 Shore OOO.
 64. The method of claim 63, wherein the gel exhibitsless than less than 10 wt % oil bleed out after being under compressionof 1.2 atm for at least 25 days at 70° C.
 65. The method of claim 63,wherein the thermoplastic rubber comprises a styrenic triblockcopolymer.
 66. The method of claim 65, wherein the styrenic triblockcopolymer is selected from the group consisting of astyrene-ethylene/butylene-styrene and astyrene-ethylene/propylene-styrene copolymer.
 67. The method of claim63, wherein the at least one additional additive comprises a mineralfiller, and wherein the mineral filler is between 0.1 wt % and 50 wt %of the overall composition.
 68. The method of claim 67, wherein themineral filler is selected from the group consisting of talc, calciumcarbonate, clay, wollastonite, silicates, glass, and combinationsthereof. 69.-70. (canceled)
 71. The method of claim 63, wherein the atleast one additional additive comprises an anti-tack agent, and whereinthe anti-tack agent is between 0.1 wt % and 10 wt % of the overallcomposition.
 72. The method of claim 71, wherein the anti-tack agent isselected from the group consisting of a silicone, silane, siloxane, orcopolymer thereof. 73.-74. (canceled)
 75. The method of claim 63,wherein the high molecular weight oil is derived from one of thefollowing: a mineral oil, a paraffin oil, a oil, an aromatic oil, apoly-alpha olefin, or a combination thereof. 76.-78. (canceled)
 79. Themethod of claim 63, wherein the stabilizer is a hindered phenolstabilizer.
 80. The method of claim 65, wherein the thermoplastic rubbercomprises a styrenic diblock copolymer.
 81. The method of claim 80,wherein the styrenic diblock copolymer is selected from the groupconsisting of styrene-ethylene/propylene diblock copolymer,styrene-ethylene/butylene diblock copolymer, and styrene butadienediblock copolymer.
 82. The gel of claim 22, wherein the thermoplasticrubber is prepared from a composition comprising a styrenic triblockcopolymer and a styrenic diblock copolymer.
 83. The gel of claim 82,wherein the styrenic triblock copolymer is selected from the groupconsisting of a styrene-ethylene/butylene-styrene (SEBS) triblockcopolymer, a styrene-ethylene/propylene-styrene copolymer (SEPS)triblock copolymer, and a styrene-butadiene-styrene (SBS) triblockcopolymer.
 84. The gel of claim 82, wherein the styrenic diblockcopolymer is selected from the group consisting of astyrene-ethylene/propylene (SEP) diblock copolymer, astyrene-ethylene/butylene (SEB) diblock copolymer, and a styrenebutadiene (SB) diblock copolymer.
 85. The gel of claim 39, wherein thestabilizer is a hindered phenol stabilizer.